This invention relates to novel compounds having the formula ##STR2## in which R is lower alkyl or lower alkoxy; R.sub.1 is lower alkyl; R.sub.2 is thio-lower alkyl or thio-lower alkenyl; R.sub.3 is hydrogen or lower alkyl and X is oxygen or sulfur; provided that when X is oxygen, R is lower alkoxy.
By the terms "lower alkyl" and "lower alkoxy" are meant such groupings having from 1 to 6 carbon atoms. Examples of lower alkyl groups are methoxy, ethoxy, isopropoxy, and isobutoxy. Examples of lower alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, and n-amyl. Preferably, the lower alkyl and lower alkoxy groups have from 1 to 4 carbon atoms. The term "lower alkenyl" includes such groupings having from 2 to 5 carbon atoms and at least one double bond. A preferred member of this group is allyl. The terms "thio-lower alkyl" and "thio-lower alkenyl" include groupings as defined under "lower alkyl" and "lower alkenyl" additionally including a sulfur atom. The thio-lower alkyl or thio-lower alkenyl group may be substituted on the phenyl ring at the ortho, meta or para position. In general, the para-substituted compounds show the highest activity.
In one embodiment of this invention, X is sulfur and R is lower alkyl; these compounds are dithiophosphonates. In another embodiment, X is sulfur and R is lower alkoxy; such compounds are dithiophosphates. In a third embodiment, X is oxygen and R is lower alkoxy, making such compounds monothiophosphates.
In another aspect, this invention relates to a method of controlling or combatting insects or mites by applying an insecticidally or miticidally effective amount of a compound as defined herein to the insect or the habitat thereof, or to a locus at which insecticidal or miticidal protection is desired.
In still another aspect, this invention relates to insecticidal or miticidal compositions of matter comprising an insecticidally or miticidally effective amount of a compound as defined herein with an insecticidally or miticidally suitable diluent or carrier.
In addition, certain of the compounds of this invention have also been found to possess plant growth regulatory activity; several compounds have also been found to be fungicides.
In general the compounds of the invention may be prepared by a three-step process.
In the first step, an aminothiophenol is reacted with a lower alkyl or lower alkenyl halide in the presence of an acid acceptor (such as triethylamine) and a solvent (such as benzene or tetrahydrofuran) to produce an amino (alkyl or alkenyl) thiophenol: ##STR3## in which R.sub.4 is lower alkyl or alkenyl, X is a halogen and R.sub.2 and R.sub.3 are as defined above.
In the second step, the product of step (a) is reacted with chloroacetic anhydride or chloroacetyl chloride in the presence of a solvent (such as tetrahydrofuran) and a base, preferably N,N-dimethylaniline, to produce a chloroacetamide-substituted thiophenol: ##STR4##
This product is then reacted with a thiophosphate or thiophosphonate (as the acid or an alkali metal salt) to produce the desired product: ##STR5## in which M is an alkali metal or hydrogen and R and R.sub.1 are as previously defined.
Reaction (c) is conducted in the presence of a base (such as triethylamine) and a solvent (such as tetrahydrofuran). All reactions are conducted at atmospheric pressure. Temperatures are in the range of 25.degree.-100.degree. C. [reaction (a)], -25.degree. to 70.degree. C. [reaction (b)], and 20.degree.-40.degree. C. [reaction (c)].